RU2065854C1 - 4-benzoyl isoxazole derivatives, process for preparation thereof, herbicidal composition, and method of controlling weeds - Google Patents

Abstract

4-Benzoyl isoxazole derivatives of general formula (I): <CHEM> wherein: R<1> represents cyclopropyl; R<2> represents -S(O)nR; R<3> represents chlorine, bromine or trifluoromethyl; R represents methyl; and n represents 2; and their use as herbicides is described. > w

Description

где R¹ означает циклопропильную группу;
R² означает -S(O)_nR;
R³ означает атом хлора, брома или трифторметильную группу;
R означает метильную группу; и
n 2;
которые обладают ценными гербицидными свойствами.The invention relates to new derivatives of 4-benzoylisoxazole containing their compositions and their use as herbicides. The invention relates to derivatives of 4-benzoylisoxazoles of the general formula (I):

where R ¹ means a cyclopropyl group;
R ² is —S (O) _n R;
R ³ means a chlorine atom, bromine or trifluoromethyl group;
R is a methyl group; and
n 2;
which have valuable herbicidal properties.

The invention relates to the following compounds:
A) 4- (4-chloro-2-methylsulfonylbenzoyl) -5-cyclopropylisoxazole;
B) 5-cyclopropyl-4- (2-methylsulfonyl-4-trifluoromethylbenzoyl) - isoxazole; and
C) 4- (4-bromo-2-methylsulfonylbenzoyl) -5-cyclopropylisoxazole.

 The letters AC are assigned to the above compounds for reference and subsequent identification.

 The compounds of the invention show unexpected and very high herbicidal activity compared to known compounds against important weeds, including foxtail (Setaria viridis and Setaria faberii), cock millet (Echinochloa crus-galli), creeping weed (Digitaria sanguinalis) and baking powder sorghum (Sorboro) .

 Compounds of general formula (I) can be prepared by known methods, for example, as described below.

 In the following description, where the symbols appearing in the formulas are not specifically defined, it should be understood that they are “previously defined” in accordance with the first definition of each symbol in the specification.

 In the process descriptions below, the sequential steps can be carried out in a different order and that suitable protecting groups can be used to obtain the desired compounds.

где L означает отщепляющуюся группу, с солью гидроксиламина. Обычно L означает О-алкильную группу, N, N-диалкиламиногруппу, например, этоксигруппу или диметиламиногруппу. Реакцию обычно осуществляют в растворителе, таком как этанол или ацетонитрил, не обязательно в присутствии основания или акцептора кислоты, такого как триэтиламин или ацетат натрия.In accordance with the invention, compounds of general formula (I) can be prepared by the reaction of a compound of general formula (II):

where L is a leaving group, with a hydroxylamine salt. Typically, L is an O-alkyl group, an N, N-dialkylamino group, for example, an ethoxy group or a dimethylamino group. The reaction is usually carried out in a solvent, such as ethanol or acetonitrile, optionally in the presence of a base or an acid acceptor, such as triethylamine or sodium acetate.

с превращением сульфенильной группы в сульфонильную группу. Окисление сульфенильной группы обычно проводят с использованием, например, 3-хлорпербензойной кислоты в инертном растворителе, таком как дихлорметан при -40 0^oС.According to the invention, the compounds of formula (I) can be obtained by oxidation of the compounds of general formula (III):

with the conversion of a sulfenyl group to a sulfonyl group. The oxidation of the sulfenyl group is usually carried out using, for example, 3-chloroperbenzoic acid in an inert solvent such as dichloromethane at -40 0 ^o C.

где Y означает карбоксигруппу или ее активную производную (такую как хлорид карбоновой кислоты или карбоновый сложный эфир) или цианогруппу, с соответствующим металлоорганическим агентом, таким как реагент Гриньяра ли литийорганический реагент. Реакцию обычно проводят в инертном растворителе, таком как простой эфир или тетрагидрофуран при температуре от 0^oС до температуры кипения смеси с обратным холодильником.According to the invention, compounds of general formula (I) can be prepared by the reaction of a compound of general formula (IV):

where Y is a carboxy group or its active derivative (such as a carboxylic acid chloride or carboxylic ester) or a cyano group, with an appropriate organometallic agent such as an Grignard reagent or organolithium reagent. The reaction is usually carried out in an inert solvent, such as ether or tetrahydrofuran, at a temperature of from 0 ^{° C.} to the boiling temperature of the mixture under reflux.

 Intermediates in the preparation of compounds of general formula (I) are prepared using known methods.

с соединением общей формулы VI:

Реакцию обычно проводят в присутствии катализатора в виде кислоты Льюиса, такого как хлорид алюминия, при температуре от комнатной до 100^oС.Compounds of general formula III can be prepared by the reaction of a compound of general formula V:

with a compound of general formula VI:

The reaction is usually carried out in the presence of a catalyst in the form of a Lewis acid, such as aluminum chloride, at a temperature of from room temperature to 100 ^° C.

где L означает отщепляющуюся группу с солью гидроксиламина.Compounds of general formula III can also be prepared by the reaction of a compound of general formula (VII):

where L is a leaving group with a hydroxylamine salt.

 Hydroxylamine hydrochloride is generally preferred. In general, L is an O-alkyl group or an N, N-dialkylamino group, for example, an ethoxy group or a dimethylamino group. The reaction is usually carried out in a solvent, such as ethanol or acetonitrile, possibly in the presence of a base or an acid acceptor, such as triethylamine or sodium acetate.

Compounds of general formula (III) can also be prepared by reacting a compound of general formula (IV), wherein Y represents a carboxy group or its reaction derivative (such as carboxylic acid chloride or carboxylic acid ester) or a cyano group with a suitable organometallic reagent such as Grignard reagent, or organolithium reagent. The reaction is usually carried out in an inert solvent, such as ether or tetrahydrofuran, at a temperature of from 0 ^{° C.} to the boiling temperature of the mixture under reflux.

(VIII)
с триалкилортоформиатом или диалкилацеталем диметилформамида. Обычно используются триэтилортоформиат или диэтилацеталь диметилформамида. Реакция с триалкилортоформиатом обычно проводится в присутствии уксусного ангидрида при температуре кипения смеси с обратным холодильником, а реакция с диалкилацеталем диметилформамида может проводиться в присутствии инертного растворителя при температуре от комнатной до температуры кипения смеси с обратным холодильником.Compounds of general formula (II) can be prepared by the reaction of a compound of general formula VIII:

(Viii)
with trialkyl orthoformate or dialkyl acetal dimethylformamide. Dimethylformamide triethyl orthoformate or diethyl acetal are commonly used. The reaction with trialkyl orthoformate is usually carried out in the presence of acetic anhydride at the boiling point of the mixture under reflux, and the reaction with dialkyl acetal of dimethylformamide can be carried out in the presence of an inert solvent at room temperature to the boiling temperature of the mixture under reflux.

с триалкилортоформиатом или диалкилацеталем диметилформамида. Реакция может быть осуществлена как описано выше для получения формулы (II) из соединения формулы (VIII).Compounds of general formula (VII) can be prepared by the reaction of a compound of general formula IX:

with trialkyl orthoformate or dialkyl acetal dimethylformamide. The reaction can be carried out as described above to obtain formula (II) from a compound of formula (VIII).

 The preparation of intermediates of the general formulas (IV), (V), (VI), (VIII) and (IX) is well described in the literature.

 The following examples illustrate the preparation of compounds of general formula (I) and the following comparative examples illustrate the preparation of intermediates of the present invention. In the present description, T. to. Denotes the boiling point, T. pl. denotes the melting point. The letters NMR mean that the spectral characteristics of nuclear magnetic resonance are indicated at this point.

 Example 1

 Compounds A, B and C.

Sodium acetate (1.93 g) was added to a mixture of 1- (4-chloro-2-methylsulfonyl-phenyl) -3-cyclopropyl-2-ethoxymethylene propane1,3-dione (8.4 g) and hydroxylamine hydrochloride (1.64 g ) in ethanol with stirring. The mixture was stirred at room temperature overnight. The mixture was evaporated and the residue was dissolved in ethyl acetate, washed with water, dried (anhydrous magnesium sulfate) and filtered. The filtrate was evaporated to dryness and the residue was recrystallized from ether to give 4- (4-chloro-2-methylsulfonylbenzoyl) -5-cyclopropylisoxazole (4.4 g) as an off-white solid. T. pl. 184 185 ^o C.

 In the same way, using the corresponding substituted starting materials, the following compounds of general formula (I) were obtained (Table 1).

 Comparative example 1.

 A mixture of 1- (4-chloro-2-methylsulfonylphenyl) -3-cyclopropylpropane-1,3-dione (7.1 g) and triethylorthoformate (6.9) in acetic anhydride was stirred and heated at the boiling temperature of the mixture under reflux for 2 hours. The mixture was evaporated to dryness and the dry residue was dissolved in toluene and again evaporated to give 1- (4-chloro-2-methylsulfonylphenyl) -3-cyclopropyl-2-ethoxymethylene propane-1,3-dione (8.4 g) in as a red resin, which was not further purified.

 In a similar manner, the following compounds were prepared using suitably substituted starting materials (Table 2).

 Comparative Example 2

 A mixture of tert-butyl 2- (4-chloro-2-methylsulfonylbenzoyl) -3-cyclopropyl-3-oxopropionate (9.5 g) and 4-toluenesulfonic acid (1.5 g) in toluene was stirred and refluxed in for 3 hours. After cooling, the mixture was washed with water, dried (anhydrous magnesium sulfate) and filtered. The filtrate was evaporated to dryness to give 1- (4-chloro-2-methylsulfonylphenyl) -3-cyclopropylpropane-1,3-dione (7.1 g) as an orange gum.

NMR spectrum (CDL ₃ ): 0.8-1.2 (multiplet, 4H), 1.5-1.9 (multiplet, 1H), 3.3 (singlet, 3H), 5.8 (singlet, 1H) 7.3-7.8 (m, 2H); 7.9 (s, 1H).

 In a similar manner, the following compounds were prepared using suitably substituted starting materials (Table 3).

 Comparative example 3.

 Carbon tetrachloride (2 ml) was added to a mixture of magnesium (0.57 g) and tert-butyl-3-cyclopropyl-3-oxopropionate (4.36 g) in methanol. The mixture was stirred for 0.5 hours. The mixture was evaporated to dryness and the residue was dissolved in toluene. The mixture was again evaporated to dryness and suspended in acetonitrile. 4-Chloro-2-methylsulfonylbenzoyl chloride (6.0 g) was added and the mixture was stirred for 3 hours. The mixture was evaporated to dryness and the residue was dissolved in ethyl acetate. The mixture was washed with an aqueous solution of hydrochloric acid (2 M), water, dried (anhydrous magnesium sulfate) and filtered. The filtrate was evaporated to dryness to give tert-butyl 2- (4-chloro-2-methylsulfonylbenzoyl) -3-cyclopropyl-3-oxopropionate (9.6 g) as a brown oil, which was not further purified.

 In a similar manner, the following compounds were prepared using suitably substituted starting materials (see Table 4).

 Benzoyl chlorides were prepared by heating appropriately substituted benzoic acids at reflux with thionyl chloride for 3 hours. Excess thionyl chloride was removed by evaporation and the benzoyl chloride thus obtained was used directly without further purification.

 Comparative example 4.

Potassium permanganate (316 g) was added with stirring to a suspension of 4-bromo-2-methylsulphenyltoluene (90.5 g) in water, while maintaining the boiling temperature of the mixture under reflux. The mixture was altered and refluxed for 3 hours. The mixture was filtered and the residue washed with hot water. The filtrate was cooled to room temperature and extracted with ethyl acetate. The aqueous solution was acidified to pH 1, saturated with sodium chloride and extracted with ethyl acetate. The organic layer was washed with water, dried (anhydrous magnesium sulfate) and filtered. The filtrate was evaporated to dryness to give 4-bromo-2-methylsulfonylbenzoic acid (44.6 g) as a light brown solid with a melting point of 220 - 220.5 ^o C.

In a similar manner, the following compound was obtained using suitably substituted starting materials:
4-chloro-2-methylsulfonylbenzoic acid;
NMR (CDL ₃ + DMSO-d ₆ ): 3.35 (singlet, 3H), 7.5-7.8 (multiplet, 2H), 7.9 (singlet, 1H), 8.2-8.6 ( broad singlet, 1H).

 Comparative Example 5

Hydrogen peroxide (30) was added to a cooled solution of 2-methylsulphenyl-4-trifluoromethylbenzoic acid (6.0 g) and acetic anhydride (3.6 ml) in acetic acid at 10 ^° C. The mixture was allowed to slowly warm to room temperature and was stirred in for 0.5 hours. The mixture was stirred and heated at 65 ^{° C.} for 3 hours. After cooling, the mixture was poured into ice water and extracted with ether. The organic layer was washed with water, an aqueous solution of iron sulfate, dried (anhydrous magnesium sulfate) and filtered. The filtrate was evaporated to dryness to give 2-methylsulfonyl-4-trifluoromethylbenzoic acid (5.54 g) as a white substance with a melting point of 155.5 156 ^° C.

 Comparative example 6.

n-Butyllithium (2.5 M solution in cyclohexane; 25 ml) was added dropwise in an inert atmosphere to a stirred solution of 4-bromo-3-methylene-sulfenylbenzotrifluoride (16.4 g) in ether at -70 ^° C for 2 hours and then the solution was poured onto granules of solid carbon dioxide. The mixture was stirred for 10 minutes and an aqueous solution of hydrochloric acid was added. The layers were separated and the aqueous layer was extracted with ether. The combined organic layers were washed with water, dried (anhydrous magnesium sulfate) and filtered. The filtrate was evaporated and the residue was triturated with cyclohexane and filtered to give 2-methylsulphenyl-4-trifluoromethylbenzoic acid (12.4 g) as a white substance;
NMR (CDL ₃ + DMSO-d ₆ ): 2.45 (singlet, 3H), 7.2 (doublet, 1H), 7.3 (singlet, 1H), 8.0 (doublet, 1H), 10.7 -11.1 (broad singlet, 1H).

 Comparative Example 7

Tert-butyl nitrite (4 ml) was added to a mixture of 5-chloro2-methylaniline (4 g) and dimethyl disulfide (26.3 g) in chloroform. After the start of the reaction, tert-butyl nitrite (17.7 ml) and 5-chloro-2-methylaniline (16 g) were added simultaneously. The mixture was stirred at room temperature for 2 hours and allowed to stand overnight. The mixture was washed with water, an aqueous solution of hydrochloric acid (2 ml), water, dried (anhydrous magnesium sulfate) and filtered. The filtrate was evaporated to dryness to give 4-chloro-2-methylsulphenyltoluene (24.6 g) as a red oil;
NMR (CDCl ₃ ): 2.2 (singlet, 3H), 6.85 (singlet, 2H), 7.0 (singlet, 1H).

In a similar manner, the following compound was obtained using suitably substituted starting materials:
4-bromo-3-methylsulphenylbenzotrifluoride with a boiling point of 84 - 88 ^o With 2 mm Hg.

 Comparative example 8.

A cooled solution of sodium nitrite (5.8 g) in concentrated sulfuric acid (50 ml) was added dropwise to a stirred solution of 4-methyl-3-methylsulphenylaniline (12.8 g) in glacial acetic acid at 20 ^° C. The resulting suspension was added to a mixture of copper (I) bromide (12 g), aqueous hydrobromic acid (48 50) and ice. The mixture was stirred at room temperature for 3 hours and then diluted with water and extracted with ethyl acetate. The organic layer was washed with water, an aqueous solution of sodium hydroxide (2 ml), dried (anhydrous magnesium sulfate) and filtered. The filtrate was evaporated to dryness. The residue was triturated with hot cyclohexane and filtered. The filtrate was evaporated to dryness to give 4-bromo-2-methylsulphenyltoluene (8.6 g) as a brown oil;
NMR (CDCl ₃ ): 2.15 (singlet, 3H), 2.2 (singlet, 3H), 6.5-7.1 (multiplet, 3H).

 Comparative example 9.

Concentrated hydrochloric acid (128 ml) was slowly added to a suspension of 2-methylsulphenyl-4-nitrotoluene (36.6 g) in methanol. While stirring, iron powder (36 g) was added while maintaining the temperature below 50 ^° C. The mixture was stirred at room temperature for 4 hours. The mixture was poured into water neutralized by the addition of sodium carbonate, filtered and the residue was extracted with dichloromethane. The aqueous layer was extracted with dichloromethane and the combined organic layers were washed with an aqueous solution of sodium chloride, dried (anhydrous magnesium sulfate) and filtered. The filtrate was evaporated to dryness and the residue was purified by silica gel column chromatography, eluting with a mixture of ethyl acetate and n-hexane, to give 4-methyl-3-methylsulphenylaniline (12.8 g) as an orange solid;
NMR (CDL ₃ ): 2.2 (singlet, 3H), 2.35 (singlet, 3H), 3.45 (singlet, 2H), 6.1-6.9 (multiplet, 3H).

 A further object of the present invention is a method for controlling weeds (i.e., unwanted vegetation) by applying a herbicidally effective amount of at least one isoxazole derivative of the general formula (I). For this purpose, isoxazole derivatives are usually used in the form of herbicidal compositions (i.e., together with compatible diluents and carriers and / or surfactants suitable for use in herbicidal compositions), for example, as described below.

 The compounds of general formula (I) show herbicidal activity against dycotyledonous (i.e. broadleaf) and monocotyledonous (i.e. grassy) weeds by application before and / or post-emergence treatment. Pre-emergence treatment means application to soil in which seeds or sprouts of weeds are present, before sprouts appear above the surface of the soil. Post-emergence treatment means application from the air or spreading in relation to weeds that have already appeared above the surface of the soil. For example, the compounds of general formula (I) can be used to control broadleaf weeds, for example, Abutilon theophrasti, Amaranthus retroflexus, Bidens pilosa, Chenopodium album, Galium aparine, Ipomoea spp. or Ipomoea purpurea, Sesbania exaltata, Sinapi arvensis, Solanum nigrum and Xanthium strumarim and grassy weeds, e.g., Alopecurus myosuroides, Avena fatua, Digitaria sanguinalis, Echinochloa crus-galli, Sorghum indicaaria or Setaria faberii or Setaria viridis and sedges, for example, Cyperus esculentus.

 The amount of the compounds of the general formula (I) used varies depending on the nature of the weeds, the composition used, the time of application, climatic and weather conditions, and (when applied to a growing crop area) the nature of the crop. When applied in areas with a growing crop, the speed of application should be sufficient to control weeds and at the same time not causing significant damage to the crop. Usually, taking into account the listed factors, the use of 0.01 5 kg per hectare brings good results. However, it should be noted that, depending on the task, larger or smaller quantities of material can be used.

 The compounds of general formula (I) can be used to selectively control weeds, for example, as mentioned above, by applying before or after emergence of the weeds in a directed or non-directional manner, for example, by directed or non-directional spraying at the site of weed growth in the area used, or when used on areas with growing crops, for example, wheat, barley, oats, maize and rice, soybeans, field and dwarf beans, peas, alfalfa, cotton, nuts, flax, onions, carrots, cabbage, turnips, sunflowers , Sugar beet, normal or planted grass, before or after planting of the crop, before or after emergence of the crop. For the selective control of weeds at the place of their growth in the used territory or territory that they are going to use to grow the crop, for example, the plants mentioned above, a suitable level of use can be 0.01 2.0 kg of active substance per hectare.

 The compounds of general formula (I) can also be used to control weeds, especially those mentioned above, by applying before or after they appear in orchards and other places of tree growth, for example, in forests, plantings and parks, and on plantations, for example sugarcane, oil palm, rubber plantations. For this purpose, they can be used in a directed or non-directional manner (for example, directed or non-directional spraying) on weeds or the soil on which they are expected to appear, before or after planting trees or plantations with a level of application of 0.25 to 5.0 kg and more preferably between 0.5 to 4.0 kg of active substance per hectare.

 The compounds of general formula (I) can also be used for weed control, especially those mentioned above, in places where there are no cereal crops, but for which weed control is necessary for any reason.

 Examples of such areas are airfields, industrial sites, railroad tracks, roadside territories, irrigation and other waterways, areas covered with shrubs and steamed lands or uncultivated lands, in particular, on which weed growth must be controlled to avoid fires. When used for such purposes in which a general herbicidal effect is often desired, the active compounds are usually used in doses greater than the doses used in areas where the crop grows, as described above. The exact dose will depend on the nature of the plants and the desired effect.

 Particularly suitable for this purpose is the use of the active substance at a level of 1.0 to 20.0 kg, more preferably 5.0 to 10.0 kg, before and after emergence of weeds, preferably before emergence, in a directed or non-directional manner (for example, directed or non-directional spray) per hectare.

 In pre-emergence treatment, the compounds of general formula (I) can be introduced into the soil on which weeds are expected. It is also useful that the compounds of general formula (I) during post-emergence treatment, i.e. when applied from air or spreading on emerging weeds, also normally contact the soil and control weeds that have not yet sprouted.

 Where a sustained release is particularly necessary, the use of compounds of the general formula (I) may be repeated if necessary.

 A further object of the invention are herbicidal compositions comprising one or more isoxazole derivatives of the general formula (I), in combination with a preferably homogeneously distributed one or more compatible agriculturally acceptable diluent or carrier and / or surfactant (i.e. with diluents or carriers and / or surfactants of the type that is suitable for use in herbicidal compositions and which is compatible with the compounds of general formula (I). The term "homogeneously distributed defined is also used to describe compositions in which the compounds of general formula (I) are dissolved in other components. The term "herbicidal compositions" is used in a broad sense, which includes not only compositions ready for direct use, but also concentrates that must be diluted before use, Preferably the compositions contain 0.05 to 90% by weight of one or more compounds of the general formula (I).

 The herbicidal compositions may contain either a diluent or a carrier, and a surfactant (i.e., moisturizing, dispersing or emulsifying) substance. Surfactants that may be present in the herbicidal compositions of the present invention may be of the ionic or nonionic type, for example, sulforicinoleates, quaternary ammonium derivatives, products based on condensates of ethylene oxide with alkyl or polyaryl phenols, for example, nonyl or octyl phenols, or esters of carboxylic acids and anhydrosorbitols, which were obtained by esterification of free hydroxyl groups by condensation with ethylene oxide, alkaline and alkaline salts Gmina Jemielno metals of sulfuric acid esters and sulphonic acids such as dinonyl- and dioktilsulfonosuktsinaty and sodium salts of alkali metals and neschelochnozemelnyh macromolecular derivatives of sulfonic acids such as sodium and calcium lignosulphonates and sodium and calcium alkylbenzene sulphonates.

 Advantageously, the herbicidal compositions of the invention comprise up to 10 weight percent. for example, 0.05 to 10 weight. surfactants, but if necessary, the herbicidal compositions in accordance with the invention may include a large proportion of surfactants, for example, up to 15 weight. in concentrates of a liquid emulsifiable suspension and up to 25 weight. in liquid water-soluble concentrates.

 Examples of suitable solid diluents or carriers are aluminum silicate, talc, calcined magnesium oxide, kieselguhr, calcium triphosphate, powdered cork, carbon absorbent and clays such as kaolin and bentonite. Solid compositions (which may be in the form of dusts, granules or a wettable powder) are usually prepared by grinding compounds of general formula (I) with solid diluents or by impregnating solid diluents or carriers into solutions of compounds of general formula (I) in volatile solvents, evaporation of solvents and, if necessary grinding products to obtain powder. Granular compositions can be prepared by absorbing compounds of general formula (I) (dissolved in suitable solvents, which can be, if necessary, volatile) solid diluents or carriers in granular form and, if necessary, by evaporation of the solvent or granular compositions in powder form, obtained as described above. Solid herbicidal compositions, in particular wettable powders and granules, may contain wetting or dispersing agents (for example, of the type described above) which, in the case of a solid, may also serve as diluents or carriers.

 The liquid compositions in accordance with the invention may be in the form of an aqueous, organic or aqueous-organic solution, suspension or emulsion, which may be supplemented with a surfactant. Suitable liquid diluents for the liquid composition include water, glycols, tetrahydrofurfuryl alcohol, acetophenone, cyclohexanone, isophorone, toluene, xylene, mineral, animal and vegetable oils and light aromatic and naphthenic oil fractions (and mixtures of these diluents). Surfactants that may be present in liquid compositions may be ionic or non-ionic (for example, of the type described above) and may, in the case of a liquid, serve as diluents or carriers.

 Powders, dispersible granules and liquid compositions in the form of concentrates can be diluted with water or other suitable diluents, for example, mineral or vegetable oils, especially in the case of liquid concentrates in which the solvent or carrier is oil, to obtain compositions ready for direct use.

 If necessary, liquid compositions of the compounds of general formula (I) can be used in the form of self-emulsifying concentrates containing active substances dissolved in emulsifying agents or in solvents including emulsifying agents compatible with the active substances, a simple addition of water to such concentrates makes the composition ready to use.

 Liquid concentrates in which the diluent or carrier is oil can be used without further dilution by means of electrostatic spray equipment.

 The herbicidal compositions of the present invention may also include, if necessary, adjuvants, such as adhesives, protective colloids, thickeners, permeation agents, stabilizers, preservatives, anti-sintering agents, coloring agents and corrosion inhibitors. These adjuvants may also serve as carriers or diluents.

Further, the percentage composition is indicated in weight percent, if this is not indicated additionally. Preferred herbicidal compositions in accordance with the invention:
aqueous suspension concentrates, which include 10 70 one or more compounds of the general formula (I), 2 10 surfactants, 0.1-5 thickeners and 15 87.9 water;
wettable powders, which include 10 90 one or more compounds of the general formula (I), 2 10 surfactants and 8 88 solid diluent or carrier;
water-soluble or water-dispersible powders, which include 10 90 one or more compounds of the general formula (I), 2 40 sodium carbonate and 0 88 solid diluent;
liquid water-soluble concentrates which include 5 50 for example 10 30 one or more compounds of the general formula (I), 5 20 surfactants and 25 90 for example 45 85 water-miscible solvent, for example dimethylformamide, or a mixture of water-miscible solvent and water;
liquid concentrates of emulsifiable suspensions, which include 10 70 one or more compounds of the general formula (I), 5 15 surfactants 0.1 5 thickeners and 10 84.9 organic solvents;
granules, which include 1 90 for example, 2 10 of one or more compounds of the general formula (I), 0.5 7 for example, 0.5 2 for a surfactant and 3 98.5 for example, 88 97.5 of a granular carrier;
emulsifiable concentrates which comprise 0.05 90 preferably 1 60 one or more compounds of the general formula (I), 0.01 10 and preferably 1 10 surfactants and 9.99 99.94 and preferably 39 98.99 organic solvent.

 The herbicidal compositions of the invention may include compounds of general formula (I) in combination, preferably homogeneously distributed, with one or more pesticidally active substances and, if desired, with one or more pesticidally acceptable diluent or carrier, surfactant or auxiliary agents, as described higher. Examples of other pesticidal compounds that can be included or used in conjunction with the herbicidal compositions of the present invention, for example, to increase the number of controlled weeds, include, for example, alachlor [2-chloro-2,6'-diethyl-N- (methoxymethyl) -acetanilide] atrazine [2-chloro-4-ethylamino-6-isopropylamino-1,3-triazine] bromoxynil [3,5-dibromo-4-hydroxybenzonitrile] chlorotoluron [N '- (3-chloro-4-methylphenyl) -N, N- dimethylurea] cyanazine [2-chloro-4- (1-cyano-1-methylethylamino) -6-ethylamino-1,3,5-triazine] 2,4-D [2,4-dichlorophenoxyacetic acid] dic mba [3,6-dichloro-2-methoxybenzoic acid] diphenesquat [1,2-dimethyl3,5-diphenylpyrazolium salts] flampropmethyl methyl [N-2 (N-benzoyl-3-chloro-4-fluoroanilino) propionate] fluoromethuron [ N '- (3-trifluoromethylphenyl) -N, N-dimethylurea] isoproturon [N'- (4-isopropylphenyl) -N, N-dimethylurea] insecticides, for example synthetic peretroids, for example permethrin and cypermethrin, and fungicides, for example carbamates, for example methyl N- (1-butylcarbamoylbenzimidazol-2-yl) carbamate, and triazoles, for example 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazole- 1-yl) -butan-2-one.

 Pesticidal compounds and other biologically active substances can be included or used together with the herbicidal compositions of the present invention, as, for example, mentioned above, and which are acids used, if necessary, in the form of derivatives, for example, salts of alkali metals and amines and esters .

 A further object of the invention is to provide products containing at least one isoxazole derivative of the general formula (I), or, preferably, herbicidal compositions as described above, preferably herbicidal concentrates, which must be diluted before use, comprising at least one isoxazole derivative general formula (I) in a container for this derivative or derivatives of general formula (I), or the named herbicidal compositions. Containers such as those commonly used for storing chemicals that are solid at normal ambient temperatures, and herbicidal compositions, especially in the form of concentrates, such as metal cans and drums that can be lacquered inside, and plastic materials, bottles and cans are used from plastic materials, and if the contents of the container are solid, for example, granular herbicidal compositions, boxes, for example, from cardboard, plastic materials and metal, or bags. The containers usually have sufficient capacity to store the amount of isoxazole derivative or herbicidal compositions, which is enough to process at least one acre of land for weed control, but not exceeding the size that is convenient to handle when implementing this method. Instructions must be physically associated with the container, for example, printed directly on it, or on an attached tag or label. Directions usually show that the contents of the container after dilution, if necessary, can be used to control weeds at a dose of 0.01 to 20 kg of active material per hectare.

The following examples illustrate the herbicidal compositions of the invention:
Example C1.

Soluble concentrate is formed from the following components:
Active ingredient (compound A) 20 wt./volume
Potassium hydroxide solution (33 wt./vol.) 10 vol./volume
Tetrahydrofurfuryl alcohol (THFS) 10 vol / vol
Water Up to 100 volumes
adding while stirring to THF, the active ingredient (compound A) and 90 volumes of water, a solution of potassium hydroxide to pH 7 8 and bringing to a predetermined volume with water.

 Similar soluble concentrates can be prepared as described above by replacing isoxazole (substance A) with other compounds of general formula (I).

 Example C2.

The wettable powder is formed from the following components, w / w:
Active ingredient (compound A) 50
Sodium dodecylbenzene sulfonate 3
Sodium Lignosulfate 5
Sodium formaldehyde alkylnaphthalene sulfonate 2
Fine silica 3
Chinese clay 37
mixing the above ingredients together and grinding them in an air-jet mill.

 Similar wettable powders can be prepared as described above by replacing isoxazole (substance A) with other compounds of general formula (I).

 Example C3

A water-soluble powder is formed from the following components, w / w:
Active ingredient (compound A) 50
Sodium dodecylbenzene sulfonate 1
Fine silica 2
Sodium Bicarbonate 47
mixing the above ingredients together and grinding them in a threshing mill.

 Similar water-soluble powders can be prepared, as described above, by replacing isoxazole (substance A) with other compounds of the general formula (I).

 Substances of the invention were used as herbicides in accordance with the following procedures.

 The method of using herbicidal compounds.

a) General
A suitable amount of the compounds used to treat the plants was dissolved in acetone to obtain solutions equivalent to using up to 4000 g of the test compound per hectare (g / ha). These solutions were applied from a standard laboratory herbicide sprayer containing 290 liters of spray liquid per hectare.

b) Pre-emergence treatment
Seeds were sown in square plastic pots with a width of 70 mm and a depth of 75 mm in non-sterile soil. The number of seeds per pot was as follows:
Weed name Approximate number of seeds per pot
1) Broadleaf weeds
Abutilon theophrasty 10
Amaranthus retroflexus 20
Galium aparine 10
Ipomea purpurea 10
Sinapis arvensis 15
Xanthim strumarium 2
2) grassy weeds
Alopecurus myosuroudes 15
Avena fatua 10
Echinochloa crus-galli 15
Setaria viridis 20
3) sedges
Cyperus esculentus 3
Cereal crops
1) Broadleaf
Cotton 3
Soya 3
2) Grassy
Maize 2
Fig 6
Wheat 6.

 The compounds of the invention were applied on the surface of the earth containing seeds, as described in paragraph (a). A pot of each cereal crop and each weed was subjected to control without spraying and spraying with pure acetone.

 After processing, the pots were placed in a capillary casing and in a glass house and were washed from above. A visual assessment of crop losses was made possible in 20 24 days. The results were presented as a percentage reduction in growth or yield loss of weeds compared to plants in control pots.

c) Post-emergence treatment
Weeds and crops were sown directly into compost (John Innes) in square pots 70 mm wide and 75 mm deep with the exception of Amarantus, which was planted in the sprout stage and transferred to the pots a week before spraying. Plants grew in a greenhouse until they were ready to be sprayed with compounds for treating plants. The number of plants in the pot was as follows (see table. 5).

 The substances used to treat the plants were applied to the plants as described in paragraph (a). A pot of each cereal crop and each weed was subjected to control without spraying and spraying with pure acetone.

 After treatment, the pots were placed in a capillary casing and in a glass house and were washed from above once after 24 hours and then with controlled subirrigation. A visual assessment of crop losses was made 20 24 days after spraying. The results were presented as a percentage reduction in growth or yield loss of weeds compared to plants in control pots.

 The compounds of the invention showed a remarkable level of herbicidal activity on the weeds used in these experiments, and at the same time tolerance to cereal crops. When used before or after the appearance of weeds, 1000 g / ha of compounds A, B, and C resulted in at least a 90-percent reduction in the growth of one or more species of weeds.

Comparison experiment
The tests were carried out in the fields of the station Spencer, Indiana, USA.

Each of the compounds was dissolved in acetone and used at doses of 100, 200 and 400 g / ha in test areas of 1 m ² using a small sprayer.

 The plots were sown with Setaria faberi, Setaria viridis, Echinochloa crus-galli, Digitaria sanguinakis and Sorghum bicolor.

 Before and after seedling application was used on different plots. Used two replications.

The activity of the compounds was assessed visually 28 days after pre-emergence and 22 days after post-emergence use (compared with untreated plots) and phytotoxicity for each treatment was evaluated at an effective dose of a. and. necessary for 90 suppression of the weed species, ED _go - expressed in g / ha (see table. 6). TTT1 TTT2 TTT3

Claims (9)

1. Derivatives of 4-benzoylisoxazole of the general formula I

where R ¹ cyclopropyl group;
R ² -S (O) _n R;
R ² chlorine, bromine or trifluoromethyl group;
R is a methyl group;
n = 2.  2. The compound according to claim 1, which is 4- (4-chloro-2-methylsulfonylbenzoyl) -5-cyclopropylisoxazole.  3. The compound according to claim 1, which is 5-cyclopropyl-4- (2-methylsulfonyl-4-trifluoromethylbenzoyl) - isoxazole.  4. The compound according to claim 1, which is 4- (4-bromo-2-methylsulfonylbenzoyl) -5-cyclopropylisoxazole. 5. A method of obtaining derivatives of 4-benzoylisoxazole of General formula I

where R ¹ cyclopropyl group;
R ² -S (O) _n R;
R ^{3 is} chloro, bromo or trifluoromethyl group;
R is a methyl group;
n = 2,
characterized in that the reaction of the compounds of General formula III

where L is a leaving group;
R ¹ , R ² and R ³ have the indicated meanings,
with hydroxylamine salt. 6. A herbicidal composition containing an isoxazole derivative as an active ingredient in a herbicidally effective amount in combination with an agronomically acceptable diluent or carrier and / or surface active agent, characterized in that it contains a 4-benzoylisoxazole derivative of the general formula I as an isoxazole derivative

where R ¹ cyclopropyl group;
R ² -S (O) _n R;
R ^{3 is} chloro, bromo or trifluoromethyl group;
R is a methyl group;
n = 2.  7. The composition according to p. 6, characterized in that the effective amount is 20 to 50 wt. active ingredient.  8. The composition according to PP.6 and 7 in the form of a soluble concentrate, water-soluble or wettable powder.  9. A method of controlling weeds in the place of their growth by applying a benzoylisoxazole derivative to the place of plant growth, characterized in that a compound of general formula I according to claim 1 is used as a benzoylisoxazole derivative at a dose of 0.1 to 4 kg / ha.

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